You will need to use the pen tool, which looks like a the nib of a fountain pen. Vectoring is limited in Photoshop as it's mainly a raster manipulation program.
What it can do is summarised in this tutorialhttp://www.teamphotoshop.com/articles-the-techniques-creating-a-vector-image-in-photoshop-5,8,101a.html
Another thing you will find is the magic wand tool and the marquee tool is superior to other programs, making transprancies is now very quick and easy. I'll will get Illustrator uploaded today.>>2070763
The Singing ED outfit from the movie.